Патент USA US2407492код для вставки
Sept- 10, 1946- 2,407,492 L. G. HALL ETAL PRODUCTION OF GASOLINE Filed June’ 11, 1945 3 :3LutvLF 23$8.: Q ?.4V . “N . Ad 9. .Q. 4% a0. .3. .LE.2 . R ..LHv~»0 8 ?gs,m ., w .0N R. HQ mm .. M .m c,1oh?.cuve az. a. na. .._ mm2.. w.\ m ma. 28mm a 9 kn‘ 6 . _ l ‘. Patented Sept. 10, 1946 I 2,4e7,492 UNITED STATES PATENT OFFICE PRODUCTION OF GASOLINE Larry G. .Hall, St. Louis, Mo., and. Herman G. Boucher, Wood River, 111., assignors to Shell De velopment Company, San Francisco, Calif., a corporation of Delaware Application June 11, 1945, SerialNo..598,708 7 Claims. (Cl. 196-50) 2 This invention relates to the ,productionof gas material and considerable depreciation of‘ the oline and especially aviation grade gasoline from anti-knock properties of the gasoline. Re?ning petroleums. More particularly the .invention re by conventional acid treating followed by doctor lates to a method of treatment whereby increased treating and rerunning has the recognized dis production of gasoline of any speci?ed quality 5 advantages of high acid consumption, poor-yields and comprising. straightrungasoline and cracked and depreciation of the anti-knock properties. gasoline may be produced from a given amount of In View .of these disadvantages such materials are petroleum. in a more economical manner. sometimes re?ned by catalytic methods referred ‘The primary aim of the. petroleum re?ner is to to generally as hydro?ning. In this re?ning produce the maximum amount of best quality 10 method'the material is treated under .hydrogen gasoline .from a. given quantity of crude petroleum ' pressure in the presenceof asuitable hydrogena tion catalyst. The chief advantage of hydro?n in the most economical manner. Thus, the cri terion of .the production obtained is not merely ing over conventional acid re?ning methods is the number of barrels of gasoline produced per that the material may be refined with. less loss of barrel of crude, nor the quality of the gasoline, 15 material. However, hydro?ning, as practiced at present, is not Wholly satisfactory. The process but a combination of these hereinafter referred to as quality-barrel. The term "quality” in this consumes considerable amounts of expensive hy expression is a weighted numerical index of qual drogen; furthermore, a considerable loss in anti knock characteristics is usually caused by the sat ity such as octane number or such other index as may-be suitable. In general the quality of gaso 20 uration of at least part. of the ole?nic and/or aromatic constituents of the gasoline. line is ?xed by specification and the re?ner then The re?ned cracked gasoline is then blended strives to produce ‘the maximum amount of ma-, with the maximum amount of the re?ned straight terial .meeting such speci?cations. . run gasoline that can be tolerated while still In ‘the usual practice the ?rst step in the pro duction of gasoline from petroleum is to separate 25 maintaining the desired quality of the blend. It will be appreciated that the re?nergusually gasolinesconstituents naturally ‘occurring therein. has at his disposal one or more additives such as This is e?ected by a simple topping operation. alkylate, isopentane, aromatic extract, cumene, The product is known as straight run gasoline. xylidine, tetraethyl lead, etc., which are usually Straight rungasoline .consists essentially of sat urated hydrocarbons and contains only small 30 added to the blend of cracked and straight run gasoline to produce the ?nal gasoline product. amounts of impurities which, due to their char However, the amount of such additives that can acter, are, jfurthermor'e, relatively easily removed. be addedxto the blend .of cracked and straight run It therefore _generally requires ‘and ' is given only gasoline (sometimes referred to as base stock) is a light acid re?ning treatment. .Straight‘run gasoline, however, generally has very poor anti 35 limited by the limited availability of the'additives or by speci?cations of such factors as heat con knock characteristics :and is consequently of poor quality. - tent, volatility, corrosiveness, and the like. The minimum quality oi’ the blend of cracked and straight run gasoline produced by the re?ner is somewhatfurther into one or more-suchproducts 40 therefore usually below that of the ?nished gaso line and is determined by‘ the amount of such ad as-kerosene, naphtha, stove .oil, gas oil, and re ditivesavailable .for use. duced crude. One or more of .these products is then cracked by various conventional cracking In the process of the present invention straight processes to produce additional amounts of gaso run gasoline and cracked gasoline are produced line. Any of the conventional cracking processes 45 from petroleum in the above described general producing an ole?nic high anti-knock gasoline manner. ‘The invention lies in the particular product may be employed. However, in conven 'methodof handling these materials to produce tional practice, catalytic cracking with clay-type the ?nished blend. The cracked gasoline may cracking catalysts is preferred since .such. proc be produced from any portion of the petroleum essesproduce gasoline of superior quality. 50 boiling above the gasoline desired and may be The cracked gasolines contain appreciable produced by any of the conventional cracking amounts of sulfur ‘compounds, nitrogen com and/or‘reforming methods which produce ahigh pounds, diole?ns, acetylenic compounds, and anti-knock ole?nic gasoline. A preferred method other materials which are di?ioult to remove by is, byythe catalytic cracking of petroleum oils ord-lnaryire?ning methods without large losses of 55 with clay-type catalyst, Such ‘processes are, for The material remaining after Ltopping to re move straight run gasoline is usually separated 2,407,492 5 the order of 200-2000pounds per square inch are illustrative. The hydrofining treatment may be advantageously carried out at temperatures rang ing from about 400° F. to about 10000 F. When the material treated is high in sulfur (for exam ple containing more than about 0.1%. sulfur) low example, the Houdry process, the Thermofor process, and the fluid catalyst catalytic cracking process. The catalysts used in these processes comprise certain selective natural clays and earths, modi?ed clays, and various synthetic clay-type catalysts. The clays are sometimes used in their natural state but are usually treated temperatures (below about 85()‘_) F.) consistent with the activity of the catalyst and the other and/or modi?ed for instance, by acid washing, treating conditions are generally preferred. removing iron-bearing impurities, leaching out- ' alumina, adjusting the ratio of silica to’ alumina, and/or by incorporating minor amounts of pro moters in order to increase their activity, stabil ity, etc., or to reduce their carbon-forming tendl ' ency. Various synthetic clay-type cracking cata lysts are also now widely used. If the material treated is low in sulfur (for exam ple containing less than about 0.1% sulfur) high er temperatures (for example, between about 850°F. and 1000°F;) may be preferred. The treat ment afforded may be the minimum treatment consistent with the desired degree of re?ning (as ‘ These catalysts consist largely of silica and/oraluminaand/or measured by the sulfur content, gum-forming magnesia and are often modi?ed by minor amounts of such materials as BzOs, AlFs, A1PO4, ZI‘Oz, etc. Also certain promoters may be in troduced along with the hydrocarbon stream en 20 effected with a minimum hydrogen consumption and results in the minimum loss of anti-knock properties. .In some cases, however, a more thor tendency, etc); this allows the treatment to be ough treatment to‘produce a substantially satu tering the reaction zone. Such promoters in clude boric oxide, hydro-gen, halides, organic hal ides, etc. The speci?c catalyst forms no part of the present invention and will not be described in further detail. rated product (particularly when operating at the higher temperature levels) may be more ad vantageous; The separated cracked gasoline fraction con sisting largely of Ce hydrocarbons is subjected to a separate non-hydrogenating re?ning treat? ' ' In these processes the oil to be cracked is con tacted, usually in the vapor phase, with the cat alyst under suitable conditions of pressure and residence time at a temperature usually‘ in the order of 750° F. to 1200° F. depending upon the ment. treatment is carried out under ‘ conditions of particular hydrocarbon feed, the particular cat alyst, and the particular results desired. acid concentration, temperature, time, etc., and in the known manner to the extent necessary to provide a suitable re?ning. The exact strength and/or amount of acid required will depend to a ' According to the process of the present inven tion there is separated from the cracked gasoline prior to further handling an ole?nic fraction consisting largely of Ceor C6-C7 hydrocarbons. certain extent upon the amount of unsaturated hydrocarbons present in the material treated and Likewise there is separated from the straight run gasoline prior to re?ning a substantially satu to a certain extent upon the conditions employed rated fraction consisting largely of Ce hydrocar bons. The separated straight run fraction is blended with the remaining cracked gasoline. Thus, the separated straight run fraction is sub s'tituted for the separated cracked fraction in the cracked gasoline. The two materials result ing'are separately re?ned and then reblended. 45 In a preferred embodiment of the invention the separated cracked fraction is also blended with ‘a remaining portion of the straight run gaso line; thus the separated cracked fraction is also ‘substituted for the separated straight run frac~ tion in the straight run gasoline. ' The catalytic gasoline containing the separated straight run fraction is mixed with a hydrogen containing gas, and contacted with a hydrogena tion ‘catalyst, i. e., hydro?ned, ‘and the blend'is subjected to the described re?né ing treatment. as a caustic solution. ' , ; . ' . This treatment may or the desired end-point. are the oxides and sul?des of V, Cr, Mn, Fe, Co, v Particularly suitable catalysts '60 comprise a sul?de of a metal of the iron group, preferably in combination with a sul?de of a _ .. . The hydro?ned blend and the acid treated product are blended together in substantially their entirety to produce the desired blend ' of cracked gasoline and straight run gasoline (base stock) having the necessary quality. To the base stock blend there is usually then added various ‘metal of group VI of the periodic system of the Examples of such preferred catalysts _ are nickel sul?de, iron sul?de, cobalt sul?de, alone and in combination with sul?des of molyb denum or tungsten. These catalysts may gen amounts of one or more additives in accordance "withtheir availability and with due regard to ‘specifications to produce the ?nal gasoline of the erally bev used substantially continuously for ‘speci?ed'quality. The j ‘ ’ Although the novel features which’ are believed to be characteristic of the process of the inven tion are ‘mentioned above and are particularly treatment is carried out in the presence of an excess of hydrogen. The amount of hydrogen employed is in general between about 1 and 30 pointed out in the claims appended hereto,_ the mols per mol of hydrocarbon feed. (Only a por tion of this hydrogen is consumed.) sure may vary over a wide range. Pressures in . After acid treating the material is usually neu tralized by washing with an alkaline reagent such may not be followed by rerunning, i. e., cutting to for this process. Examples of suitable catalysts The pres- The separated cracked gasoline fraction may, in general, be more advantageously treated in a blend with a remaining portion of the straight ‘run gasoline. Thus, according to a preferred embodiment of the invention the separated cracked fraction is blended with a. portion of the .blendedwith' the remaining cracked gasoline) The hydro?ning ‘ , hundreds of hours without regeneration. used and since such methods are well known there is no need to describe them in detail. being the remaining tolerable straight run mate rial above the separated straight run fraction catalysts commonly employed and recommended elements. in the treating step. Any suitable method of contacting the gasoline with the acid may be remaining straight run gasoline (such portion treatment may be carried out with any of the Ni, M0 and W. A preferred treatment is a conventional acid re?ning treatment, for example, with sul furic acid or spent alkylation acid (HzSOi). The . . process. ‘may. perhaps be better understood by 75 ‘referring to the‘ following'mor'e detailed descrip monies tioneintwliichispeci?o preferred embodiments are setforth. To assist in this description-reference i’s“ had to thee-attached? drawing-wherein there is shown» byeconventional \?'gures" a: simpli?ed2 flow an: overheadiproduct-aa: cracked gasoline fraction consisting; largely of? Ge: hydrocarbons: which‘. is ' removed‘lvia line/>31.“ The: stripped absorber oil i'slrecycledit‘o theiabsorbe'rlvia. line 30.1 diagram of a‘: typi’cali applicationiof the’ process oftheinvention: > ' '6 stripping- column 3>61are1adjustedftoremoveas The liquid hydrocarbon from . separators- 252' is ' passed Via; liner- 385150. a - fractionatin'g‘ columns 392.. The‘ conditions in; fractionatin'g.v column; 39, are‘ 7 adjusted? to: remove;v as . air-‘overhead product 1 'sub‘» Referring to the’ drawing; theefeed‘ent‘ering via line 2l-is- topped topping; column: I5 to= recover overheadaelightrstraight run-fraction’ containing» stantially: all ‘of the: materialiup through normal hexane? This-overhead product removedlviakline' 4 Qii'sL passed to aisecondl- fractionating: columna 4"]; whereinzit isaseparated: into a‘: lower: boiling rfrace tion»; consisting: of products! boiling’. up: through normallpentaneiwh-iclr is: removed'cviazline 43 and substantiallyall‘; of ' the C6’ hydrocarbons and if‘ desired-1 a“ portion’ of the; C’FHXdi'OCaI'B'OIIS; ' This overheadfifraction-is ‘passed via= line 3-tb fraction atin‘gr column 4'5v wherein-i it» is separated? int'o»a l'ow‘er'b'oi-ling overheadl fraction containing’ subf stant'ially'all' of-‘theconstituentsup through» pen taneW-hichi's'withdraWn via line 45,1- andi a higher boiling "fractione consistingflargely' of ‘theéstrai'ght aehigher'boiling fraction; consisting. large-13b 0131616 hydrocarhonsawhich is removedtvialine?; This ‘ (3s .fra‘c-ti‘oniis :combin'ed : with the 1 crackediCs; fraca run‘ (‘it hydrocarbons‘ which is withdrawn’ via line 6% The‘lower boiling*ma’terial'fwitlidrawn‘via tioni removed from: the > stripper? 35 via; line; 3:1; ized cracked gasoline as hereinafter described:v .' ,- Thdcrackedigasoline fromwl'ii'chthe?Cs hydro: carboni fraction: has: been) ‘removed, is; withdrawn from fractionating columnist): via line 44; This material; may: be; out? to; a: desired end-point in line/ 5} may be-vtreatedi andi/orj utilized in any die-‘ 20 The: combined fractions; are; blendect with: the straight: run- material; and separately: treated; as sired‘ manner. The: straight I run; fraction with hereinafter described-s ' drawn vial line’ 6-1is=combined with the» d‘eliexan Thez toppedi feediremovedf from column‘ I5 via line T is- passed‘ to- a," fractionatin'g column 8 wherein» a/further -' portion‘ of straight? runligaso fractionatingmolumn 451. The overhead product line-is separated? The. amount of straightrun from: fractionator? 4'51- withdrawn ,viailinei 46; iSEthB crac-lsed:v gasoline; fractiom from. which the: Cathy; gasoline separated‘ and‘ removedloverhead‘ v-iarline 9 is preferably adjusted with respecttuthemax imum tolerable amountotstraight run gasoline 3O tobe included in the ?nished gasoline. Thus, for example, in a typical operation the material removedifrom fractionating~column 8 via 1ine 9 _ may- heme an- endepoint ~of, for. instance 185i’ E. This material vis combined; with the.- cracked. C‘s 35 fraction as‘ hereinafterdescrib'edi drocarbonshavesbeenzsubstantially remoyedsn The Ca; hydrocarbom fraction removed; from the crackedrgasoline as hereinbeforeadescribediisisuba stitutefd? on'replace'd; by: the: straight: run fraction separated: ‘as; hereinbefore: described‘... ‘Bhusg, the straightrun: fractionawithdrawrr, from: fractionate ing. column ; 4: viazlinet» 6., is; blended; with; the ; CV81‘? head; product: from: fractionating; column 45. The bottom product" irom f‘ractionazton 81?. is passed via 1ine~ Hi-toa furtherefractionatingrcol; This blend: is; mixedi with: an ; excess of: hydrogen (with respect to that required;f0r;:~complete;sate umn H to remove additio‘nalg'materialisuch: as naphthankerosene, or the. like. Such“ materials 40 uration‘: of: thergasolinel' entering'via‘line 41.; For example; the, amountazof' hydrogen: introduced ~I Via areremoved overheadvialine l2 and may be line~ It?" may bGLG? molsvper mol of hydrocarbon treatedand/o'r used in anydesired?manner. The feed. Tliexmixture preheated.‘ to: a suitable‘; re higher,boilingresiduefrom fractionator. H" (re action; temperatures (for example-850? F2) in ‘a duced crude)? is passed‘vialinessw' and‘ If to a suitable- preheat‘en' 48'.- and:' passedtto catalytic: re suitable heater l5'and tar separator‘ l6. Heavy actor: 49.». Reactor 49 contains acsuitablerhydroe residue or ‘taro is removedpvia line I'L vaporized g'enatiorr-dehydrogenationz catalyst~~ such, __ for.‘ ex material'i'stllenpassed'via, line l8 ‘to a cracking ample; as; at pelleted :7 mixture‘ of nickel: sul?de reactor, [9? wherein it is cracked in theconven tungsterr sul?de; The‘ conditions/of,‘ pressure. and tional‘manner. with one ofithe conventional clay contactrtimeamay be. adjusted: to. effect. a: sub t‘ypei cracking,‘ catalysts, The; cracked‘ product stantiall‘v:v complete hydrogenation of the. ole?ns. leaves 'thelcracking reactor via line‘ 20‘ and passes Under such: conditions; the": sulfur; compounds to a, ?'actionatingwcolumn' 2'!‘ wherein the con and/or:- nitrogerr compounds: will' be; 1argely,»re. vertedllproducts are separated from‘ unconverted moved or: decomposed: and; a1so= dehydrogenation and'insuf?cientl'y. converted material; This'late ofinaphthenicz» constituents of: .theefeed may; take t'er. material may be withdrawn Via‘ line" 22"v or place. Typical conditions; are,‘ for example; a ‘recyclediin Whole or in. part‘ Vi'a. line; 13‘ to" the pressure-50f aboutz850 p.- s. ihandeatliquid hourly The converted products con cracking reactor. space velocity of‘. about 4. The productwithdrawn sistingessentially of gasoline and‘ gases passes viaelineillrv is passed to a‘conventional separating over-lieadfrom fractionator" 21' viailine' 24 to a cooler 25 and‘separator. 2B‘; The 'vaporous product from separator 26 is withdrawn via linet2'l», compressed by compressor 28, and passed to a typical adsorption system. Thus», this vaporous product" is contacted under 'pressurelini absorber'2‘9 with a suitable naphtha 60 ,andlrecoveryisystemillustrateddiagrammatically in..the drawing by a single separator 5|. Gas rich inhydrogeniswithdrawn from the; separator 5| and recycled via pump 52" and line 41. Inv order to maintain a suitable concentration of‘hydrogen or=oil1 fraction recirculated’ via" line 38‘. Dry: gas 'in‘ther recycle" gas some of this’ gas'may'be with drawn? from‘ the‘ system‘ via line 53' and‘ make-up is' removedfrom'the absorbers-via line*3l., The absorber liquid‘ containing: the absorbed; hydro; ' hydrogen may beadded‘ via-‘lineiil. The hydro ?ned: blend- of ‘ crackedi and‘ straight run gasoline withdrawn from separator 5| via‘line '5 S'isblended 33?. The‘conditions:instrippin'gg-column 33; are 70 with theacid‘ treated blend or straight‘ run gaso line and" cracked’ gasoline as hereinafter described adjusted’ to=remove as'an overhead product sub‘ and treated? by suitable means‘ to: remove hydro stantially all "of they absorbed‘ material up through gen' sul?de“ formed in' the- hydro?ning ‘treatment. normal pentane; which‘ product is removed’ via Thus, the hydro?nedi gasoline is :mixed with causa line 341. The. absorber- oilithen- passes via'line 35 to a further stripping'co‘lumn-36. ,Tlieconditions 75 ti’c'» solution= entering-1- viaeline- 56: and. passed tm a carbon-s’ passes via line 32>; to a: stripping column 2,407,492 7 8 caustic treater 51.‘ The product is withdrawn to is a very desirable and most advantageous method a settler 58. Caustic solution is recycled via line The principal advantage of the process of the 56. Make-up caustic is added via line 59. invention is that it allows the production of gaso The straight ,run gasoline from which the C6 line of any speci?ed quality (in which a blend hydrocarbons, and if desired also some of the C7 of straight run gasoline and cracked gasoline hydrocarbons, have been removed as hereinbe can be used-and this is in nearly every case) to fore described (withdrawn from fractionating col be appreciably increased without increasing the umn 8 via line 9) is blended with‘the combined catalytic Cs fractions separated as hereinbefore hydrogen requirement. Thus, for example, in a de?ned (entering via lines 3'! and 42). This blend 10 typical plant producing, for instance, about 9,000 B./D. of aviation base stock with a consumption passes via line 31 to an acid treater 60 wherein of 1.57 million cubic feet hydrogen the produc it is contacted with sulfuric acid, spent alkyla tion may be increased between about 100 and 400 tion acid, or other suitable acid under conditions B./D. In many instances the increased produc chosen with respect to the particular feed to af ford the degree of re?ning required for the par 15 tion may also be obtained with decreased oper of operation. ~ ' V I ticular gasoline being produced. In the produc ating expenses. tion of automotive gasoline, for example, a very volume production is not desired the advantage mild re?ning treatment at low temperature and with relatively dilute acid may be su?‘icient. In of the process of the invention may be realized either in the production of an equal volume of gasoline of improved quality or in the produc tion of an equal volume of gasoline of equal qual ity with decreased consumption of more costly additives. The advantage of the described method of oper the production of certain types of aviation gaso line, on the other hand, a relatively severe treat ment with a more concentrated acid may be re quired. The acid treated material is withdrawn to a separator Bl. Acid is recycled via line 62. Make-up acid is added via line 63. The acid treated material is withdrawn from the separator via line 64. This material is combined with the If for some reason increased ation in a typical case is illustrated in the fol lowing example in which it is assumed that a re?ner with the following materials available de— sires to produce the maximum amount of ANF-28 hydro?ned blend of cracked and straight run ma aviation gasoline: terial from line 55 and is neutralized in the caus tic scrubber 51. The ?nished blend or base stock 30 Example I consisting of straight run gasoline and cracked gasoline properly re?ned and in the desired pro portions is withdrawn via line 65. In general a portion of the cracked C5 fraction is included in the ?nished gasoline. This material requires a caustic treatment to remove mercaptans and hy drogen sul?de. This material, withdrawn via line . Material Depentanized straight run base stock... ‘ _ Available B _/D_ 4, 000 Catalytic cracked depentanized base sto Catalytic cracked C5 fraction _________ __ ___ 900 Isopentane (95%) ____________________________________ __ 1,840 Debutanized C4-C5 alkylate ___ 6, 450 34, may be blended with the gasoline entering umene __________________________________________ __ l, 000 the caustic treater. Hydrogen (million cubic feet) ______________________ _. l. 57 It will be appreciated that the system described 40 above and illustrated in the drawing is merely a In normal operation (case 1) 4000 B./D.'of typical example of the process of the invention depentanized catalytic cracked base stock is hy and may be modi?ed in various particulars. For dro?ned, 1000 'B./D. of depentanized catalytically example, the hydro?ned blend and the acid treat ed blend may be caustic treated separately and ‘3 cracked base stock is acid treated, 1621 B./D. of depentanized straight run base stock is acid each or both of them may be cut to the desired treated. The products are then blended. The gasoline end-point (rerun) prior to the ?nal maximum production of ANF-28 aviation gaso blending. Also, for example, in actual practice line is 15,265 B./D. When operating according to the separation and recovery system illustrated by the process of the invention (case 2) the cata the simple separator 5! may be complicated by ' a system for removing hydrogen sul?de from the lytically cracked Cs fraction andthe straight run recycled hydrogen stream and/ or by the utiliza tion of multiple compression and cooling steps. Also, the combinations of fractionating equip of 4,500 B./D. of dehexanized catalytically cracked base stock and 1,000 B./D. of the straight ment and method of handling to recover and sep arate the speci?ed fractions may be altered With out departing from the spirit of the invention. It is not essential that the cracked gasoline and Cs fraction are exchanged as described. A blend run hexane fraction is hydro?ned. A blend of 254 B./D. of catalytically cracked C's fraction and 1,150 B./D. of hexanized straight run base stock is acid treated. The materials are then blended. The maximum production of ANF-28 aviation straight run gasoline be derived from the same 60 gasoline is 15,625 l3./D. Thus, case 2 affords an petroleum. The straight run fraction, for exam increased production of 360 B./D. ple, may be derived from any, preferably naph Example II thenic, petroleum while the cracked gasoline may be derived from the cracking or reforming of Petroleum was topped to- recover a straight run any'feed stock. Also, the separation of the re 65 gasoline fraction and various intermediates. spective Cs fractions may be altered or adjusted Catalytically cracked gasoline was produced from to afford the optimum production of gasoline ac various heavy petroleum products by the ?uid cording to the circumstances. For example, the catalyst cracking process using the present com straight run fraction containing C's hydrocarbons mercial silica-alumina composite cracking cata may be cut to include a considerable portion of C7 hydrocarbons and may be cut in such a man ner as to be relatively concentrated in Cs and C7 naphthenes. When the straight run gasoline con tains appreciable amounts of naphthenic hydro_ lyst. The straight run gasoline was fractionated to recover separately a fraction consisting essen tially of Ce hydrocarbons and then rerun to an end-point of about 185° F. The catalytically cracked product was treated to recover catalyti .carbons (and most straight run gasolines do) this 75 cally cracked C5 hydrocarbons and catalytically 2,407,492 10 cracked Cc hydrocarbons separately and topped arating from a cracked gasoline an ole?nic frac tion consisting largely of C6 hydrocarbons, replac to produce a dehexanized catalytically cracked gasoline having an end-point of about 325° F. ing said separated ole?nic fraction with a satu rated straight run gasoline fraction concentrat ed in C6 and C7 naphthenes, subjecting the thus produced blend of said dehexanized cracked gaso The dehexanized catalytically cracked gasoline was blended with the straight run C6 fraction to produce a feed blend having the following prop erties: line and straight run gasoline fraction to a hy dro?ning treatment under hydrogen pressure in . Feed the presence of a hydrogenation catalyst, sub Product 10 jecting said separated ole?nic fraction to an acid Gravity, API _________________ .. ASTM distillati IBP . . . . _ . . . _ _ .____ 55. 5 50. 6 _ _ _ __ 142 152 170 208 278 172 204 280 re?ning treatment, and recombining the acid re ?ned material with the hydro?ned blend. : _. ___ _ _ 10%.... 50?". 90?". E. P Sulfur, % w_____ Unsaturates, % w . _ _ _ . _ Aromatics, % w ______ __ BON, + 4.6 cc. TEL-__ Index N0. + 4.6 cc. TE 315 15 .010 312 .088 _ _ _ ._ _ 3. In the production from petroleum of gasoline comprising straight run gasoline and cracked gas 38. 5 5. 8 30. 4 ________ __ ________ __ 34. 5 93.0 117 This blend was hydro?ned with a nickel sul?de tungsten sul?de catalyst under the following ap proximate conditions: Temperature ______________________ __°F__ 900 Pressure _________________ ___ ____ ._-p. s. i__ 840 Liquid hourly space velocity _____________ __ 4 -Mol ratio of hydrogen to hydrocarbon____; 6:1 oline, the improvement which comprises separat ing from a cracked gasoline an ole?nic fraction consisting largely of Ce hydrocarbons, separating from straight run gasoline a saturated fraction consisting largely of Ce hydrocarbons, blending 20 said latter fraction with the remainder of the cracked gasoline, subjecting the blend to a hy dro?ning treatment under hydrogen pressure in the presence of a hydrogenation catalyst, blend , ing said ole?nic fraction separated from the cracked gasoline with the remainder of the straight run gasoline, subjecting this latter blend to an acid re?ning treatment, and blending the two thus-treated gasolines. The product had the properties speci?ed in the above table. The catalytically cracked fraction consisting essentially of Ce hydrocarbons was blended with the straight run gasoline remaining after the separationof the C6 fraction. This ‘ 4.7In the production from petroleum of gaso line comprising straight run gasoline and cracked gasoline, the improvement which comprises sep arating from a cracked gasoline an ole?nic frac tion consisting largely of C6 hydrocarbons, sep arating from straight run gasoline a saturated fraction relatively concentrated in C6 and C7 blend was treated with about 20 pounds per bar rel of spent alkylation acid, caustic washed and rerun. The losses were about 18%. The acid treated blend was then blended with the hydro ?ned blend to produce the final blend or base naphthenes, blending said latter fraction with the remainder of the cracked gasoline, subjecting the blend to a hydro?ning treatment under hydrogen stock‘ pressure in the. presence of a hydrogenation cat ‘ We claim as our invention: 1. In the production from petroleum of gaso line comprising straight run gasoline and cracked gasoline, the improvement which comprises sep arating from a cracked gasoline an ole?nic frac tion consisting largely of Ce hydrocarbons, replac ing said separated ole?nic fraction with a satu alyst, blending said ole?nic fraction separated from the cracked gasoline with the remainder of .the straight'run gasoline, subjecting this latter blend to an acid re?ning treatment, and blend ing the two thus-treated gasolines. 45 5. Process according to claim 1 in which the cracked gasoline is a catalytically cracked gaso rated straight run gasoline fraction consisting lineobtained by cracking a hydrocarbon oil with largely of C6 and C7 hydrocarbons, subjecting the a clay type cracking catalyst. . . thus produced blend of said dehexanized cracked 6. Process according to claim 1 in which the gasoline and straight run gasoline fraction to a 50 hydro?ning treatment is carried out with a hy hydro?ning treatment under hydrogen pressure drogenating metal sul?de catalyst. at a tempera in the presence of a hydrogenation catalyst, sub ture of about 850° F. and 1000° F. jecting said separated ole?nic fraction to an acid 7. Process according to claim 1 in which the re?ning treatment, and recombining the acid re acid re?ning treatment is carried out under mild ?ned material with the hydro?ned blend. conditions to leave the major portion of the ole 2. In the production from petroleum of gaso- I ?ne intact. line comprising straight run gasoline and cracked ' LARRY G. HALL. V . gasoline, the improvement which comprises sep ‘HERMAN G. BOUCHER.